CN110620234A - High-potential lithium ion battery NCA ternary cathode material and preparation method thereof - Google Patents
High-potential lithium ion battery NCA ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of lithium ion batteries, and particularly relates to a high-potential lithium ion battery NCA ternary cathode material and a preparation method thereof, which overcome the defect that the layered high-nickel-cobalt lithium aluminate NCA and derivatives thereof of the lithium ion battery cathode material have poor electrochemical cycle performance, particularly the defect of extremely poor cycle performance under the condition of high cut-off voltage. The molecular expression of the anode material of the invention is Li (Ni)0.8+x+yCo0.15‑xAl0.05‑y)1‑z‑kSizO2@(Li2SiO3)k，0<x<0.15，0<y<0.05，0<z + k is less than or equal to 0.2; it has high specific discharge capacity, excellent circulating stability and capacityThe preparation method adopts the traditional solid phase method to firstly dope the precursor body phase to inhibit the generation of microcracks and then automatically generate Li through the reaction with surface residual alkali2SiO3The coating layer of the lithium ion conductor is fast, the operation is simple, the industrial production is easy, the purity of the prepared product is high, the chemical uniformity is high, the crystallization quality is high, the product particles are fine and are uniformly distributed, the electrochemical performance is excellent, and the manufacturing cost is lower.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium ion battery anode material and a preparation method thereof, in particular to a lithium ion battery anode material Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kAnd a process for the preparation thereof, wherein 0<x<0.15，0<y<0.05，0<z+k<0.2。
Background
The lithium ion battery has the characteristics of high energy density, small self-discharge, excellent cycle stability, no memory effect and the like, so that the lithium ion battery becomes a part of the power battery field in the new energy automobile industry at present. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte, wherein the positive electrode material is one of the key materials of the lithium ion battery, and the performance of the positive electrode material directly determines the performance of the lithium ion battery; the positive electrode material is also the most costly component in lithium ion batteries; how to improve the energy density and the safety of the anode material and prolong the service life of the lithium ion battery is the key for determining whether the lithium ion battery can be applied on a large scale.
Lithium ion batteryThe main current industrialization of the anode material is as follows: lithium cobaltate, lithium manganate, lithium iron phosphate and ternary cathode materials; the NCA and the NCM belong to the same ternary cathode material, and the NCA ternary cathode material mainly comprises: li (Ni)0.8+x+yCo0.15-xAl0.05-y)O2And derivatives thereof; in order to meet the requirement of the market on the energy density of the anode material, the ternary anode material is developed in the positive direction of high nickel (Ni is more than or equal to 0.6), the NCA belongs to the high-nickel ternary anode material, and the molar Ni content of the NCA is more than 80 percent at present. The current market puts higher requirements on the energy density of NCA, and the increase of the cut-off voltage of the anode material is a feasible method; however, as the cut-off voltage increases, the side reaction is increased, and the cycle stability of the material is reduced sharply. And a number of studies have shown that: the main reasons for the reduction of the cycle performance of the material are that after the material is cycled for many times, a large number of microcracks are generated by the active material on the anode plate, so that the polarization of the material is increased, the impedance is increased, and the electrolyte permeates into the microcracks to cause short circuit and the like.
Disclosure of Invention
The invention aims to provide a layered high nickel cobalt lithium aluminate NCA (Li (Ni) for a lithium ion battery positive electrode material0.8+x+yCo0.15-xAl0.05-y)O2) And derivatives thereof, especially the defect of extremely poor cycle performance under the condition of high cut-off voltage, and provides high-valence Si for inhibiting the generation of microcracks in the cycle process4+Gradient bulk doping incorporating surface auto-generated Li2SiO3Coating modified lithium ion battery anode material Li (Ni)0.8+x+yCo0.15- xAl0.05-y)1-z-kSizO2@(Li2SiO3)kAnd a process for the preparation thereof, wherein 0<x<0.15，0<y<0.05，0<z+k<0.2. The lithium ion battery anode material has higher specific discharge capacity and excellent cycle stability, can meet the requirement of long cycle of charge and discharge with larger multiplying power, and is prepared by adopting the traditional solid phase method to firstly dope a precursor body phase to inhibit the generation of microcracks and then automatically generate Li with surface residual alkali2SiO3Fast lithium ionThe conductor coating layer is simple to operate and easy for industrial production, and the prepared product has high purity, high chemical uniformity, high crystallization quality, fine and uniform product particles, excellent electrochemical performance and lower manufacturing cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
the NCA ternary cathode material of the high-potential lithium ion battery is characterized in that the molecular expression of the NCA ternary cathode material of the high-potential lithium ion battery is Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kWherein x is more than 0 and less than 0.15, y is more than 0 and less than 0.05, 0<z + k is less than or equal to 0.2, and k < z >; @ denotes Li2SiO3Coated with Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2A surface.
The lithium ion battery anode material Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kThe preparation method is characterized by comprising the following steps:
step 1, using absolute ethyl alcohol or pure water as dispersing agent and using (Ni)0.8+x+yCo0.15-xAl0.05-y)(OH)2And the derivative thereof is a precursor, and the precursor and a silicon source are mixed according to the molar ratio: (1-z-k) and (z + k) are uniformly mixed, ground uniformly and dried to obtain a mixture 1;
step 2, taking absolute ethyl alcohol or pure water as a dispersing agent, and mixing a lithium source and the mixture 1 obtained in the step 1 according to the mol ratio: (1-1.15), uniformly mixing the raw materials 1, grinding uniformly, and drying to obtain a mixture 2;
and 3, placing the mixture 2 in a tube furnace, heating to 480-580 ℃ at the speed of 3 ℃/min for pre-sintering for 6-12 h in an oxygen atmosphere, heating to 750-900 ℃ at the speed of 2 ℃/min for roasting for 15-24 h, naturally cooling to room temperature, grinding and sieving the product to obtain the Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kWherein, 0 < x <0.15，0＜y＜0.05，0<z + k is less than or equal to 0.2, and k < z >.
In step 2, the lithium source raw material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium oxide and lithium hydroxide.
In step 1, the silicon source material is at least one of silicon dioxide, nano silicon dioxide, silicon tetrachloride, ethyl orthosilicate, ethyl metasilicate, orthosilicate and metasilicate.
The invention uses high valence state Si4+Fast lithium ion conductor Li with ion phase doping and automatic generation2SiO3Coating combination, and doping small amount of Si into nickel cobalt lithium aluminate (NCA)4+Ion (0)<z + k is less than or equal to 0.2) isomorphous substitution, Si4+Then automatically generating fast lithium ion conductor Li with surface residual alkali2SiO3Surface coating is carried out, thus obtaining the lithium ion battery anode material Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)k(ii) a On the one hand, small amount of Si4+The ionic phase is doped, and a cross-linking structure (like concrete) formed by silica-oxygen bonds of the ionic phase improves the stability of the internal structure of the material, and inhibits the generation of surface microcracks; on the other hand, the surface residual alkali is consumed due to the action of the silicon dioxide and the surface residual alkali, so that the surface alkalinity is reduced, and the material processing performance is improved; surface generated Li2SiO3For Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2Surface coating is carried out, surface side reaction is inhibited, the surface stability is improved, and the lithium ion conductivity of the material is improved, so that the ternary cathode material (Li (Ni) compared with nickel cobalt lithium aluminate (NCA)) is obtained0.8+x+yCo0.15-xAl0.05-y)O2) Li (Ni) with more stable structure0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kAnd has higher specific capacity and more excellent cycling stability. In addition, Li2SiO3The surface is coated withThe silicon dioxide and the surface residual alkali are automatically generated, so the coating amount is far less than that of Si4+The doping amount is k < z >.
In summary, the invention has the following advantages:
1. layered Li (Ni) prepared by the invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kLithium ion battery positive electrode material passing through very small amount of tetravalent Si4+Position of ionic phase doping substitution transition metal, and automatically generated layered fast lithium ion conductor Li2SiO3The surface of the material is coated, so that the internal structure of the material is stabilized, the generation of microcracks on the surface of the material is inhibited, and the cycle performance of the material is improved; meanwhile, the surface coating also reduces the side reaction between the material surface and the electrolyte, enhances the transmission rate of lithium ions in the anode material, and improves the electrochemical performance, especially the rate capability of the material.
2. The invention adopts a solid phase mixing method to carry out bulk phase doping on the precursor, can realize more uniform bulk phase doping dispersion through long-time grinding, overcomes the defect of insufficient environmental protection of the traditional liquid phase synthesis method, and automatically generates Li2SiO3The chemical uniformity of the coating layer is good, and the thickness of the formed coating layer is extremely thin.
3. The high-voltage anode material Li (Ni) prepared by the invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kThe material has higher specific discharge capacity and excellent cycle performance; under the room temperature environment, when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the first discharge specific capacity of the lithium ion battery anode material can reach 185.8mAh g-1178.9mAh g can be achieved after the circulation is carried out for 101 times-1The capacity retention rate is 96.3%; when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 198.8mAhg-1185.9mAh g after circulating for 101 times-1The capacity retention rate is as high as 93.5%.
4. The preparation process of the invention has no toxic and harmful substances, is environment-friendly, has simpler production equipment related in the process, and is easier to realize large-scale industrial production.
Drawings
FIG. 1 shows Li (Ni) of lithium ion battery prepared by the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kA process flow chart of the anode material.
FIG. 2 shows Li (Ni) of lithium ion battery prepared by the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kXRD pattern of the positive electrode material.
FIG. 3 shows Li (Ni) of lithium ion battery prepared by the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kSEM image of the positive electrode material.
FIG. 4 shows Li (Ni) of lithium ion battery prepared by the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kThe positive electrode material is in a cycle performance diagram of charging and discharging at 0.2C multiplying power within a voltage range of 2.75-4.30V.
FIG. 5 shows Li (Ni) of lithium ion battery prepared by the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kThe positive electrode material is in a voltage range of 2.75-4.50V, and a 0.5C multiplying power charge-discharge cycle performance curve chart.
FIG. 6 shows Li (Ni) prepared in comparative example of the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kAnd (3) a cycle performance diagram of charging and discharging at 0.2C multiplying power within a voltage range.
FIG. 7 shows Li (Ni) prepared in comparative example of the present invention0.8Co0.15Al0.05)O2Positive electrode materialA cycle performance diagram of charging and discharging with 0.5C rate in a voltage range of 2.75-4.50V.
FIG. 8 shows Li (Ni) of lithium ion battery of the present invention0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kThe positive electrode material and the particles of the comparative example were cut in cross section (after 101 cycles).
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings.
Example 1
When the total doping amount of Si is 0.02, namely z + k is 0.02, 8.9776g of self-made (Ni) is weighed according to the measurement0.80Co0.15Al0.05)(OH)2Precursor, 0.1208g Nano SiO2Uniformly mixing, fully grinding uniformly by using alcohol as a dispersing agent, drying in a blast oven and grinding to obtain a mixture 1; using alcohol as dispersant, 4.5545g of lithium hydroxide monohydrate (LiOH. H) was weighed2O) and is fully mixed with the mixture 1 obtained before, evenly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 500 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 16h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the lithium ion battery anode material (shown in figure 1).
The XRD test was performed on the above lithium ion battery positive electrode material, and the result is shown in fig. 2; the material has a perfect layered structure, the cation mixed-arrangement degree is extremely low, no impurity phase exists, and the space group is R3 m.
The result of SEM test on the above lithium ion battery positive electrode material is shown in fig. 3; the material is in the form of more regular spherical particles with a few attachments on the surface, which is Li2SiO3And (7) coating.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material has higher specific discharge capacity and excellent cycling stability; at room temperature (Under the environment of 25 +/-2 ℃), when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the initial discharge specific capacity of the lithium ion battery anode material can reach 185.8mAh g-1178.9mAh g can be achieved after the circulation is carried out for 101 times-1The capacity retention rate was 96.3% (as shown in fig. 4); when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 198.8mAh g-1185.9mAh g after circulating for 101 times-1The capacity retention rate was as high as 93.5% (as shown in FIG. 5).
Example 2
When the total doping amount of Si is 0.03, namely z + k is 0.03, 8.8860g of self-made precursor and 0.1812g of nano SiO are weighed according to the measurement2Uniformly mixing, fully grinding uniformly by using alcohol as a dispersing agent, and then placing in a drying oven for drying and grinding to obtain a mixture 1; using alcohol as dispersant, 4.5545g of lithium hydroxide monohydrate (LiOH. H) was weighed2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 500 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 800 ℃ at the speed of 2 ℃/min for roasting for 15h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; under the environment of room temperature (25 +/-2 ℃), when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the first discharge specific capacity of the lithium ion battery anode material can reach 182.5mAh g-1176.1mAh g can be achieved after circulation for 101 times-1The capacity retention rate is 96.5%; when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 192.3mAh g-1The product can still reach 180.2mAh g after being circulated for 101 times-1The capacity retention rate is as high as 93.7%.
Example 3
When the total doping amount of Si is 0.02, namely z + k is 0.02, 8.9766g of self-made (Ni) is weighed according to the measurement0.86Co0.10Al0.04)(OH)2Weighing ethyl orthosilicate in proportion, adding the ethyl orthosilicate into a proper amount of absolute ethyl alcohol, uniformly mixing, adding the mixture into the precursor, fully and uniformly grinding the mixture by taking alcohol as a dispersing agent, and then placing the mixture into a drying oven to dry and grind the mixture to obtain a mixture 1; using alcohol as dispersant, 4.5545g of lithium hydroxide monohydrate (LiOH. H) was weighed2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 480 ℃ at the speed of 3 ℃/min for presintering for 8h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 16h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; under the environment of room temperature (25 +/-2 ℃), when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the first discharge specific capacity of the lithium ion battery anode material can reach 183.8mAh g-1After circulating for 101 times, 175.7mAh g can still be achieved-1The capacity retention rate is 95.6%; when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 198.2mAh g-1184.7mAh g can be achieved after the circulation is carried out for 101 times-1The capacity retention rate is as high as 93.2%.
Example 4
When the total doping amount of Si is 0.03, namely z + k is 0.03, 8.8852g of self-made (Ni) is weighed according to the measurement0.86Co0.10Al0.04)(OH)2Weighing ethyl orthosilicate in proportion, adding the ethyl orthosilicate into a proper amount of absolute ethyl alcohol, uniformly mixing, adding the mixture into the precursor, fully and uniformly grinding the mixture by taking alcohol as a dispersing agent, and then placing the mixture into a drying oven to dry and grind the mixture to obtain a mixture 1; alcohol is used as dispersant4.5545g of lithium hydroxide monohydrate (LiOH. H) were weighed2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 480 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 18h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; under the environment of room temperature (25 +/-2 ℃), when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the first discharge specific capacity of the lithium ion battery anode material can reach 181.7mAh g-1177.5mAh g after 100 times of circulation-1The capacity retention rate is 97.7%; when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 191.6mAh g-1After circulating for 101 times, 179.5mAh g can be achieved-1The capacity retention rate is as high as 93.7%.
Example 5
8.6104g of self-made (Ni) are weighed according to the measurement when the total doping amount of Si is 0.06, namely z + k is 0.060.90Co0.08Al0.02)(OH)2Weighing ethyl orthosilicate in proportion, adding the ethyl orthosilicate into a proper amount of absolute ethyl alcohol, uniformly mixing, adding the mixture into the precursor, fully and uniformly grinding the mixture by taking alcohol as a dispersing agent, and then placing the mixture into a drying oven to dry and grind the mixture to obtain a mixture 1; using alcohol as dispersant, 4.5546g of lithium hydroxide monohydrate (LiOH. H) was weighed2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 480 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 18h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the target lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; it is shown that silicon modification still has a good effect of inhibiting the generation of microcracks on the high-nickel NCA material.
Example 6
When the total doping amount of Si is 0.12, namely z + k is 0.12, 8.0610g of self-made (Ni) is weighed according to the measurement0.90Co0.08Al0.02)(OH)2Weighing ethyl orthosilicate in proportion, adding the ethyl orthosilicate into a proper amount of absolute ethyl alcohol, uniformly mixing, adding the mixture into the precursor, fully and uniformly grinding the mixture by taking alcohol as a dispersing agent, and then placing the mixture into a drying oven to dry and grind the mixture to obtain a mixture 1; using alcohol as dispersant, 4.5548g of lithium hydroxide monohydrate (LiOH. H) was weighed2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 480 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 18h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the target lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; it is shown that while the increase in modified silicon content is somewhat less comparable to the capacity, it is more evident from the cycle performance that the increase in modified silicon content has a better and more pronounced effect on the high nickel NCA material in inhibiting the generation of microcracks.
Example 7
When the total doping amount of Si is 0.18, namely z + k is 0.18, 7.5114g of self-made (Ni) is weighed according to the measurement0.90Co0.08Al0.02)(OH)2Weighing ethyl orthosilicate in proportion, adding the ethyl orthosilicate into a proper amount of absolute ethyl alcohol, uniformly mixing, adding the mixture into the precursor, fully and uniformly grinding the mixture by taking alcohol as a dispersing agent, and then placing the mixture into a drying oven to dry and grind the mixture to obtain a mixture 1; using alcohol as dispersant, weighing4.5548g lithium hydroxide monohydrate (LiOH. H)2O) and the mixture 1 obtained in the previous step are fully and uniformly ground and dried to obtain a mixture 2; and finally, putting the dried mixture 2 into a tube furnace, heating to 480 ℃ at the speed of 3 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 400ml/min), heating to 780 ℃ at the speed of 2 ℃/min for roasting for 18h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the target lithium ion battery anode material.
The lithium ion battery anode material is subjected to constant current charge and discharge test, and the test result shows that the anode material still has higher specific discharge capacity and excellent cycling stability; it is shown that when the modified silicon amount is increased to the content of the embodiment, the contrast capacity is obviously influenced, and the specific capacity is obviously reduced, but the effect of the increased modified silicon amount on the high-nickel NCA material for inhibiting the generation of microcracks is still better and more obvious from the cycle performance.
Comparative example
9.1608g of self-made (Ni) are weighed according to the measurement0.80Co0.15Al0.05)(OH)24.5545g of lithium hydroxide monohydrate (LiOH. H) was weighed out2O) and mixing with the mixture, fully and uniformly grinding the mixture by using alcohol as a dispersing agent, and drying the mixture to obtain a mixture; placing the dried mixture into a tube furnace, heating to 500 deg.C at a speed of 3 deg.C/min for presintering for 6h under oxygen atmosphere (oxygen flow rate of 400ml/min), heating to 780 deg.C at a speed of 2 deg.C/min for calcining for 16h, naturally cooling to room temperature, taking out the material, grinding, and sieving to obtain Li (Ni)0.8Co0.15Al0.05)O2And (3) a positive electrode material.
For Li (Ni)0.8Co0.15Al0.05)O2Constant current charge and discharge tests are carried out, and the test result shows that the anode material has higher first discharge specific capacity but poorer cycle stability; under the environment of room temperature (25 +/-2 ℃), when the voltage range is 2.75-4.30V and the constant current charge-discharge multiplying power is 0.2C, the first discharge specific capacity of the lithium ion battery anode material can reach 188.1mAh g-1The specific discharge capacity after the circulation for 101 times is 143.9mAh g-1Capacity retention ratio of76.5% (as shown in FIG. 6); when the voltage range is 2.75-4.50V and the constant current charge-discharge multiplying power is 0.5C, the initial discharge specific capacity of the lithium ion battery anode material can reach 199.9mAh g-1The specific discharge capacity after the circulation for 101 times is only 131.5mAh g-1The capacity retention rate was as high as 65.8% (as shown in FIG. 7). Pure Li (Ni) was found unmodified0.8Co0.15Al0.05)O2Under the condition of high voltage, although the initial discharge specific capacity is high, the cycle performance is poor, and the main reason is that a large number of microcracks are generated in the pole piece in the high-voltage cycle process (as shown in fig. 8), so that the cycle performance is reduced sharply.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (4)
1. The NCA ternary cathode material of the high-potential lithium ion battery is characterized in that the molecular expression of the cathode material is Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kWherein x is more than 0 and less than 0.15, y is more than 0 and less than 0.05, 0<z + k is less than or equal to 0.2, and k is less than z.
2. The preparation method of the high-potential lithium ion battery NCA ternary cathode material according to claim 1 is characterized by comprising the following steps:
step 1, using absolute ethyl alcohol or pure water as dispersing agent and using (Ni)0.8+x+yCo0.15-xAl0.05-y)(OH)2And the derivative thereof is a precursor, and the precursor and a silicon source are mixed according to the molar ratio: (1-z-k) and (z + k) are uniformly mixed, ground uniformly and dried to obtain a mixture 1;
step 2, taking absolute ethyl alcohol or pure water as a dispersing agent, and mixing a lithium source and the mixture 1 obtained in the step 1 according to the mol ratio: (1-1.15), uniformly mixing the raw materials 1, grinding uniformly, and drying to obtain a mixture 2;
and 3, placing the mixture 2 in a tube furnace, heating to 480-580 ℃ at the speed of 3 ℃/min for pre-sintering for 6-12 h in an oxygen atmosphere, heating to 750-900 ℃ at the speed of 2 ℃/min for roasting for 15-24 h, naturally cooling to room temperature, grinding and sieving the product to obtain the Li (Ni)0.8+x+yCo0.15-xAl0.05-y)1-z-kSizO2@(Li2SiO3)kWherein x is more than 0 and less than 0.15, y is more than 0 and less than 0.05, 0<z + k is less than or equal to 0.2, and k is less than z.
3. The method for preparing the NCA ternary cathode material of the high-potential lithium ion battery according to claim 2, wherein in the step 2, the lithium source raw material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium oxide and lithium hydroxide.
4. The preparation method of the ternary cathode material of the high-potential lithium ion battery NCA according to claim 2, wherein in the step 1, the silicon source raw material is at least one of silicon dioxide, nano-silicon dioxide, silicon tetrachloride, tetraethoxysilane, orthosilicate and metasilicate.
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